Tourmaline composite grains and apparatus using them

ABSTRACT

Tourmaline fine powders are mixed with glass powders having melting point between 500° C. and the transition temperature of tourmaline, and the grains are formed from the mixture and sintered at a temperature below melting point of the glass. Tourmaline powders are stacked in the glass matrix in the tourmaline composite grains prepared above. When water passes through a case including many such grains, the water contacts with the grains and is converted to activated water by the grains. By using the activated water, a structure such as a moving vehicle or an outer wall of a building can be washed efficiently without a detergent. Further, the grains can be used in an apparatus for recycling wash water.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to composite grains of tourmaline, aproduction method thereof, and an apparatus using the tourmalinecomposite grains for example to supply wash water.

2. Description of Prior Art

Tourmaline is a mineral represented with a chemical formula, NaX₃ Al₆(BO₃)₃ Si₆ O₁₈ (OH)₄. It is divided into iron tourmaline (X=Fe), lithiatourmaline (X=Li+Al) and magnesia tourmaline (X=Mg), and mixed crystalsthereof are generated. Usually tourmaline including iron tourmaline as amain component is available most. In the crystal structure, ions of Na,Li, Al, Fe etc. are arranged in a network structure of Al₂ O₃ --B₂ O₃--SiO₂. As to electric properties of tourmaline, piezoelectricity andpyroelectricity were found in 1980, and it is known to have permanentelectric poles. These properties vanish at about 1,000° C. Tourmaline isan infrared rays radiator, and the wavelength of infrared radiations isequal to or larger than 10 μm at room temperature.

Tourmaline is used for example to remove electrostatic charges by mixingit into synthetic fibers, using electrical properties thereof and tosubject water itself to surface activation in water processing. Othervarious uses have also been proposed.

A tourmaline particulate as described in Japanese Patent laid openPublication 3-118894/1991 comprises tourmaline fine powders and a binder(or highly electrically insulating ceramics), where the tourmaline finepowders are embedded in the ceramics. The amount of the tourmaline finepowders in the particulates is about 5-10% of the entire amount, inorder to maximize the number of tourmaline electric poles existing onthe surface of the particulates while not canceling the opposite chargesby contact to each other. However, such prior art tourmalineparticulates, for example, do not have a satisfactory degree of surfaceactivation effect. Therefore, it is desirable to solve various problemsin order to use tourmaline in various uses effectively.

In general, a structure such as an automobile, a railroad train, anairplane or an outer wall of a building exposed to an outdoorenvironment is washed to remove dirt due to adherence of dust, oil ormud. When such a structure is washed, a detergent or a drug is used toimprove washing performance. For example, an automobile is washed toremove dirt adhered on the body thereof, and it is waxed thereafter toimprove its luster and to suppress adhesion of dust or the like.

When washing with a detergent or a drug is repeated, however, thesurface of the structure is changed in quality or deteriorated by thedetergent. For example, the coating on the body of an automobile isdeteriorate and loses its luster. Further, because a large amount ofdetergent is used in the washing of large structures, the water qualityin a river, a lake, a pond or an inland sea becomes worse if thedetergent is not processed sufficiently in sewage systems and the like.It is also a problem that water resources are used wastefully,especially in the times of water shortage.

Further, underground water or well water is often used in the washing ofsuch structures because of the low cost. In such a case, it is a problemthat green moss grows on the surface of the structures. Therefore, it isdesirable that structures are washed effectively while keeping luster ofthe surface thereof.

SUMMARY OF THE INVENTION

An object of the invention is to provide a material including tourmalinehaving better properties and a production method thereof.

An object of the invention is to provide a water supplier by using amaterial including tourmaline.

In one aspect of the invention, tourmaline composite grains according tothe invention comprise a glass matrix, and powders of tourmaline aredispersed therein of weight ratio which is equal to or larger than 30%.Because such a very large amount of tourmaline powders are dispersed inthe glass matrix, the tourmaline powders are in contact with each other.Then, there is a large probability that tourmaline powders are alignedin series. The lower limit of 30% denotes a limit where tourmalinepowders are dispersed while being in contact in series in the matrix.Though the upper limit is not described, there exists a practical limitfor having a sufficient strength with the glass matrix, for exampleabout 70% in an embodiment which will be explained below.

In another aspect of the invention, a water supply apparatus forsupplying wash water comprises a tank for storing raw water, a watersupplier which supplies the raw water stored in said tank, and a towercontaining the above-mentioned tourmaline composite grains. The towerreceives the raw water supplied from the tank by the water supplier, andmakes the raw water flowing therethrough to contact with the tourmalinecomposite grains. Thus, raw water is converted to activated water bycontacting with the tourmaline composite grains, and the activated watercan be supplied.

In a further aspect of the invention, an apparatus for recycling watercomprises a tank for storing waste water after washing, and a towerwhich contains the above-mentioned tourmaline composite grains. Thetower converts water received from the tank to activated water bycontacting the water to the tourmaline composite grains and supplies theactivated water for washing. Preferably, a preprocessor is providedbetween the tank and the tower for processing the waste water forimproving the activation in the tank. A washing machine may be connectedto the tank for washing an object physically with the activated water.

An advantage of the present invention is that the ionization of water isenhanced largely.

Another advantage of the present invention is that the washingperformance of water is enhanced largely.

A further advantage of the present invention is that water can berecycled efficiently.

A still further advantage of the present invention is that a structuresuch as an automobile can be washed with a physical means without adetergent.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other objects and features of the present invention willbecome clear from the following description taken in conjunction withthe preferred embodiments thereof with reference to the accompanyingdrawings, and in which:

FIG. 1 is an X-ray diffraction chart of tourmaline powders of the (a)sample not sintered, (b) sample sintered at 800° C. and (c) samplesintered at 1,000° C.;

FIG. 2 is a schematic diagram of arrangement of tourmaline fine powdersin a composite grain;

FIG. 3 is an X-ray diffraction chart of tourmaline composite grains(tourmaline: glass=7:3);

FIG. 4 is an X-ray diffraction chart of tourmaline composite grains(tourmaline: glass=7:3);

FIG. 5 is an X-ray diffraction chart of tourmaline composite grains(tourmaline: glass=5:5);

FIG. 6 is an X-ray diffraction chart of tourmaline composite grains(tourmaline: glass=3:7);

FIG. 7 is an X-ray diffraction chart of tourmaline composite grains(tourmaline: glass=2:8);

FIG. 8 is an X-ray diffraction chart of tourmaline composite grains(tourmaline: glass=1:9);

FIG. 9 is an electron microscope photograph of tourmaline compositegrains (tourmaline: glass=7:3);

FIG. 10 is an electron microscope photograph of tourmaline compositegrains (tourmaline: glass=3:7);

FIG. 11 is an electron microscope photograph of tourmaline compositegrains (tourmaline: glass=1:9);

FIG. 12 a graph of far infrared emissivity of (d) a sample of tourmalineonly, (e) a sample of tourmaline composite grains combined with a lowmelting point glass of the lime-magnesium-alkali system and (f) a sampleof tourmaline composite grain combined with low melting point glass ofzinc-alkali system;

FIG. 13 is a graph of a spectral transmittance curve (far infraredabsorbance curve);

FIG. 14 is a sectional front view of an apparatus for supplying washwater;

FIG. 15 is a sectional front view of an inner cylinder in the apparatusfor supplying wash water;

FIG. 16 is a plan view of the inner cylinder;

FIG. 17 is a schematic diagram of an apparatus for washing a motorvehicle;

FIG. 18 is a sectional front view of a tower for decomposing organicsubstances in the apparatus for washing a motor vehicle; and

FIG. 19 is a sectional front view of a tower for activating water in theapparatus for washing a motor vehicle.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring now to the drawings, wherein like referenced charactersdesignate like or corresponding parts throughout the views, first,tourmaline composite grains according to a first embodiment of theinvention is explained. In this embodiment, by pulverizing selectedtourmaline with a conventional industrial process, particles oftourmaline in a size range obtainable with the industrial process(tourmaline fine powders of median size of about 1.0 μm) are heated upto a temperature between 450 and 800° C. (in correspondence to thetransition temperature of tourmaline) and is cooled thereafter.

In an example, selected tourmaline sand (0.5 mm) is pulverized to grainsof median size of about 1.0 μm to prepare fine powders, and the finepowders are sintered in an electric furnace at 600, 700, 800, 900, 1000and 1100° C. for four hours, and cooled gradually thereafter. Thesamples prepared at the different sintering temperatures as well as acomparison example of fine powders not sintered are measured with powderX-ray diffraction.

In an X-ray diffraction chart shown in FIG. 1, reference signs "a", "b"and "c" represent a sample not sintered, a sample sintered at 800° C.and a sample sintered at 1000° C. respectively. The samples not sinteredand sintered at temperatures at and below 800° C. (including the samples"a" and "b") show diffraction peaks due to the crystal structure oftourmaline, and this means tourmaline exists in the samples. Further,peaks due to different crystal structures are not recognizedpractically. Still further, the X-ray diffraction angles (2θ) and X-rayintensities are almost the same in these samples. On the contrary,samples sintered at and above 900° C. (including sample "c") do not showdiffraction peaks (2θ) due to the crystal structure of tourmaline, ortheir intensities are low, and this means tourmaline is transformed to adifferent mineral. According to the results of X-ray diffractionexplained above, it is found that there exists a temperature around 850°C. at which the crystal structure of tourmaline is destroyed or atemperature (transition temperature) at which tourmaline is transformedto a different material.

Further, in order to study performance of the tourmaline samples forionizing water, oil decomposition is observed as follows. Powders of 15mg of the sample not sintered, and the samples sintered at 600, 700, 900and 1000° C. are put in polyethylene beakers of 230 ml, respectively.Further, 200 ml of water and 2 ml of cooking oil are added to each ofthe beakers. They are stirred for two minutes twice a day. The degree ofoil decomposition is observed for six months. The oil is decomposed inthe order from emulsifying to a rubber-like viscous state to a lowviscosity state and a gruel state. It is found that the degree of oildecomposition (decomposition speed) is large in the order of the samplesintered at 600 or 800° C., the sample not sintered, the sample sinteredat 900° C. and the sample sintered at 1000° C. Therefore, there is adifference also in the degree of oil decomposition between above andbelow the transition temperature of tourmaline.

In the crystal structure of tourmaline, ions of Na, Li, Al, Fe etc. arearranged in a network structure of Al₂ O₃ --B₂ O₃ --SiO₂. By heating,positive charge at one end of a crystal and negative charge at the otherend thereof are increased due to exchange of ionic valence (Fe²⁺ →Fe³⁺),new displacement of atomic positions or the like, and this results in acell of higher electric potential. It is considered that if the heatingtemperature exceeds 900° C., the crystal structure of tourmaline isdestroyed and the electric potential due to the displacement vanishes.Even if tourmaline is used as a raw material, electric properties oftourmaline are not used. Further, after strong drying (heating at orbelow 400° C.), energy thereof is small, and no new displacement arisesin raw tourmaline. Therefore, heating operation from 450° C. totransition temperature (850° C.) is needed for increasing electricpotential in each tourmaline grain. Especially, sintering at temperaturein a range between 600 and 800° C. is preferable.

It is said that tourmaline has permanent electric poles from the onsetof its formation. In one theory, when tourmaline is created due tometamorphism, the crystal structure is distorted from the stable statedue to rapid cooling to generate positive and negative electric poles atthe two ends of a crystal. However, tourmaline is created mainly at thelast stage of pegmatite, and large crystals are formed due to gradualcooling. Though the electric poles are created due to the distortion ofthe crystal lattice, it is considered that the magnitude of the strainscatters among them. Then, one of the methods for enhancing the chargesof the poles or electric potential in tourmaline is to cause a largemovement or shift in tourmaline crystals having piezoelectricity andpyroelectricity by adding a large energy, within a range where thecrystal structure is not destroyed. As a means for the movement orshift, the following are considered to be used: Valence change of Fe²⁺or the like included in tourmaline due to pulverizing, mechanicalthermal energy or heating, change in ionic radius according to valencechange, and physical energy of expansion or contraction due to heatingor cooling. In this embodiment, heating is used to improve theproperties of tourmaline fine powders not sintered, to providetourmaline composite grains which have superior ionization performancefor water.

Next, tourmaline composite grains are explained. FIG. 2 showsschematically a series arrangement of tourmaline fine powders 2 in theglass matrix 4. A tourmaline composite grain consists of a large amount(equal to or larger than 30%) of tourmaline fine powders 2 and a glassmatrix (binder) 4. In such a grain, the tourmaline fine particles 2exist not only on the surface of the grain, but are connected in seriesinside the grain, and this enhances the electric potential therein. Inorder to produce a tourmaline sintered material of this structure,tourmaline is pulverized to provide tourmaline fine powders, and theyare mixed with glass powders having melting point between 500° C. andthe transition temperature of tourmaline. Then, the composite mixture isformed into grains, and the grains are sintered at a temperature lowerthan the melting point of the glass.

As explained above, the glass matrix is made of glass powders having amelting point between 500° C. and the upper transition point oftourmaline. Concretely, the glass matrix is sintered at a temperaturebelow the melting point of the glass powders. At the sintering, thetourmaline powders are also sintered at the same time at a temperaturebetween 450° C. and the upper transition temperature, and this improvesthe properties of tourmaline in the matrix. The upper limit of thetemperature is set so as to prevent the crystal structure of tourmalineto be destroyed which makes the desired properties of tourmaline lost.The temperature of lower limit of 450° C. is the lowest limit at whichthe sintering effect is expected in a conventional furnace. Thesintering improves washing performance or the like of the tourmalinecomposite grains.

Concretely, in order to prevent adhesion due to melting, the sinteringtemperature is set to a temperature lower than the melting point by 50°C. or more. The obtained tourmaline composite grains are sinteredmaterials, and they are preferable for uses such as washing whichrequire porosity. Further, the sintering of the glass serves also as thesintering of tourmaline between 450° C. and the transition temperatureof tourmaline (preferably between 600 and 800° C.), and as alreadyexplained above, the sintering improves the properties of the tourmalinefine powders.

When the tourmaline composite grains are produced, tourmaline sands arepulverized to provide fine powders thereof, the tourmaline fine powdersare mixed with glass powders having melting point between 500° C. andthe transition temperature of tourmaline, and the mixture is formed intograins. Then, the grains are sintered at a temperature below the meltingpoint of the glass powders (preferably between 450 and 800° C.). Thesintering is performed at a temperature below the melting point of theglass powders in order to improve work efficiency by preventing adhesionof the tourmaline composite grains. Porousness due to sintering isadvantageous for washing. Details will be explained later.

Each of the tourmaline fine powders is an electric cell having plus andminus electric poles (+-). However, as the amount of tourmaline finepowders is increased, there appear many series connection such as(+-)(+-)(+-) . . . of the plus and minus poles of tourmaline inside asintered grain and on the surface thereof. Thus, the probability thatthe electric potential is increased becomes larger. At the same time, itis inevitable that parallel distribution and reverse connection such as(+-) (-+) are increased in proportion to the amount of tourmaline. It issaid that the potential difference of one tourmaline is 2-10 eV. Theelectric potential of a commercial cell is 1.5 V, and the electricaldecomposition voltage of water is 1.0 V (1 V≈10¹⁹ eV). In order toincrease the electric potential of the sintered grain as close aspossible to the above value, it be necessary that (1) the tourmaline ispulverized as finely as possible, to provide the largest magnitude ofelectric potential for a asingle cell, and (2) as much of the tourmalinebe collected as possible. In this embodiment, tourmaline fine powders 2of median size of about 1.0 μm which can be pulverized with aconventional industrial process, and the particles 2 are connected asmuch as possible in the sintered grains to increase the entire electricpotential. As shown schematically in FIG. 2, a minus pole at the bottomof a particle 2 contacts with a plus pole at the top of a next particle2, and a minus pole at the bottom of the particle 2 contacts with a pluspole at the top of a further particle 2, and so on. Thus, manytourmaline fine powders 2 are connected in series. Though there areisolated powders and electrically neutralized ones, the grains areproduced to increase connections so as to enhance the entire electricpotential. Thus, it is necessary to distribute the tourmaline powdershomogeneously in the binder 4, and it is preferable to form grains byusing water-containing material pulverized and mixed with a wet process.

A glass powder of low melting point (of dielectric constant of about4-8) is adopted as the binder for sintering. This binder has meltingpoint of 500-850° C., similar to the heat treatment temperature range ofthe tourmaline fine powders 2 explained above this binder also hassimilar composition to tourmaline. That is, the binder can perform theheating for generating electric potential of tourmaline, and thecollection and fixing of tourmaline fine powders at the same temperaturesimultaneously. The binder is fine powder having a composition similarto tourmaline (SiO₂, B₂ O₃, Al₂ O₃, MgO, ZnO etc.) and having beentransformed to glass already. The thermal conduction and the expansioncoefficient thereof are about the same as those of tourmaline, and theshift in the tourmaline crystals is generated smoothly. The glasspowders can sinter a large amount of tourmaline powders (between about30% and 70%) at a temperature near the melting point. The upper limit ofthe tourmaline component is a value at which the fixing with the binderis possible, and the strength of fixing is maintained to about 70%. Thelower limit of 30% is a value to which advantages of the invention areconfirmed and the tourmaline fine powders are arranged in series. It isconsidered that the grains can be used practically even if the amount isless than 30%.

Next, the method for producing the composite grains of tourmaline isexplained. The tourmaline sand and the low melting point glass powdersof weight ratio between 3:7 and 7:3 are added with a small amount ofsurface activation agent and a solid substance, and an equal amount ofwater. These consituents and mixed in a tronmel sufficiently. Theobtained slurry is filtered. Then, the obtained water-containingmaterial is formed into grains of desired shape with a forming machine,a granulating machine or the like, and the grains are dried. Next, thegrains are sintered and hardened at a temperature near the melting pointof the glass powders.

The production proceeds in detail as will be explained below. First, 50kg of tourmaline sands obtained by pulverizing selected tourmaline tomedian size of about 1.0 μm are put in a 100 kg tronmel with 50 litersof water and pulverized for 24 hours. Next, 50 kg of the low meltingpoint glass powders (for example, SiO₂ of 1.4 mol, B₂ O₃ of 1.0 mol, Al₂O₃ of 0.2 mol, MgO, CaO, Na₂ O of 0.75 mol, melting point of 750° C.)which have been prepared are added thereto, and water is added further.Then, the pulverizing is continued further for 24 hours. Thewater-containing material taken out and filtered is formed as bars of φ9 mm and length of 1000 mm with a push former. Pieces of length of 9 mmobtained by cutting it are subjected to processing with a machine forgranulation, and they are dried. Next, they are put in a sheath andsintered at 700° C. to produce grains of φ 7 mm.

FIG. 3 is a powder X-ray diffraction chart of a tourmaline compositegrain (tourmaline: glass=7:3) produced as explained above wherein theabscissa 2θ is the X ray diffraction angle. In FIG. 3, diffraction peaksdenoted with "T" are ascribed to tourmaline, and this means thattourmaline exists and has not deteriorated. It is to be noted thatdiffraction lines of the matrix 4 do not appear because the matrix is aglass.

Next, in order to study the capacity of the granular sintered materialfor ionizing water, the capacity of the oil decomposition is observed.The sample grains used for observation have three kinds of weight ratioof tourmaline to glass of 3:7, 5:5 and 7:3, prepared as explained above.By putting 15 g of the sample grains in a 200 ml polyethylene containerand adding 200 ml of water and 2 ml of cooking oil thereto, the degreeof oil decomposition is observed for two months by stirring for twominutes twice a day. According to the results, the decomposition processof emulsifying→rubber-like viscous state→low viscous state→gruel stateproceeds efficiently in the order of weight ratio of 7:3>5:5>3:7, as theresistance on stirring decreases and turbidity increases. This meansthat oil decomposition proceeds faster as the amount of tourmalineincreases.

When tourmaline contacts with water, the reaction mechanism isconsidered as follows: The electric potential of tourmaline makes waterionized as follows:

    2H.sub.2 O=H.sub.3 O.sup.+ +OH.sup.-.

As the electric potential increases, the number of ions is increased.The hydronium ions H₃ O⁺ lose charges when they contact with a metal ora resin container, and OH⁻ (or hydroxim ions H₃ O₂ ⁻) concentration isincreased in water. The tourmaline composite grains enhance ionizationbesides the ionization of water, and this increases H₃ O⁺ and OH⁻concentrations, decomposes and reacts cations H₃ O⁺ to enhance OH⁻concentration. Thus, the capability of washing is increased, and thiscan be used in industries for water washing of an object such as amechanical part.

For example, if the container is made of a metallic iron or an ironalloy (such as stainless steel), the oxidation proceeds as follows:

3Fe+6H₃ O⁺ →3Fe(OH)₂ +6H₂,

2Fe(OH)₂ +2H₃ O⁺ →2Fe(OH)₃ +2H₂, and

2Fe(OH)₃ +Fe(OH)₂ →Fe₃ O₄ +4H₂ O.

To sum up, the following reaction occurs:

3Fe+8H₃ O⁺ →Fe₃ O₄ +8H₂ +4H₂ O.

That is, Fe is oxidized with H₃ O⁺ to Fe²⁺, and converted further toFe(OH)₂ with OH⁻ (H₃ O.sup. →OR⁻ +H₂). A part of Fe(OH)₂ is oxidizedfurther with H₃ O⁺ to Fe(OH)₃. The resultant Fe(OH)₃ reacts with theremainder of Fe(OH)₂ to Fe₃ O₄ in a passive state. Then, H₂ and OH⁻concentrations are increased in water (in correspondence to consumed H₃O⁺). If O₂ dissolves in water, H₂ consumes it to H₂ O, to preventoxidation of iron. These actions passivate the inside of a metalliccontainer and a pipe with H₃ O⁺ ions, and suppresses the format of redmud by the consumption of the dissolves O₂ in water with resultant H₂.The latter is useful for water in a cooling tower for preventing red mudinside pipes.

If water flowing in a resin container or a resin pipe contacts with theresin surface, friction charges (negative charges) are given to thesurface. They are neutralized with H₃ O⁺ charges in water, so that OH⁻concentration is increased in water. The washing capability of soap, asalt of a weak acid and a strong base, is caused by hydrolysis of soapto generate OH⁻ and to produce an alkaline water. In the case oftourmaline, OH⁻ concentration is increased similarly to perform similaraction.

By using a similar production process, grains are produced in a widerange of ratios of tourmaline to glass, and powder X-ray diffraction ismeasured thereon. FIGS. 4-8 show powder X-ray diffraction charts oftourmaline composite grains produced with weight ratios of tourmaline toglass of 7:3, 5:5, 3:7, 2:8 and 1:9. Similarly to FIG. 3, the abscissa2θ represent X-ray diffraction angle, and diffraction peaks denoted with"T" are ascribed to tourmaline. The existence of tourmaline is confirmedin the weight ratio range between 3:7 and 7:3 of tourmaline to glass, asexplained above. No diffraction peak due to different crystal structuresare observed. Diffraction peak due to tourmaline are also observed insamples outside the above range.

The colors of these samples is changed as the composition is changed.The surfaces of the samples are observed with an electron microscope. Asrepresentatives, FIGS. 9-11 show electron microscope photographs oftourmaline composite grains produced with ratio of tourmaline to glassof 7:3, 3:7, and 1:9 respectively wherein a white line for a scale of 50μm is included. In these photographs, white portions correspond totourmaline, while black portions correspond to glass. The grains aresintered materials, and they are all found to be porous.

Next, a difcfoerent embodiment of the invention is explained. Tourmalineis a far infrared radiator. In order to enhance the emissivity, glasshaving high far infrared emissivity is selected as the low melting pointglass powder used for combining the tourmaline powders. Usually, it issufficient to select as the binder glass powders having a skeleton ofsilicic acid-boric acid-alumina and added lime, magnesia and alkali.However, in order to enhance infrared emissivity, glass powders having alow melting point (550° C.) are prepared which include mainly silicicacid-boric acid-alumina and zinc and alkali. The compounding ratio istourmaline powders:glass powders=1:1. The compounded material is formedinto discs of φ 50 mm and thickness of 2 mm, and they are sintered at700 and 500° C.

Far infrared emissivity is measured on the prepared tourmaline compositediscs. The measurement is performed on the above-discs at surfacetemperature of 140° C. with an apparatus having two black body furnacesof FT-1R (JIR-5300 of Nippon Densi). FIG. 12 shows far infraredemissivity of these samples, wherein (d) denotes a comparison sample oftourmaline only, (e) denotes a sample of tourmaline composite graincombined with the low melting point glass of lime, disc and alkalisystem and (f) denotes a sample of tourmaline composite disc combinedwith the low melting point glass of zinc-alkali system.

According to the data, far infrared emissivity at a wavelength of 8 μm(10.5 μm if converted at room temperature by adding 2.5 μ) is about 80%for a black body for sample (d) of tourmaline only, 90% for sample (e)of tourmaline composite disc combined with the low melting point glassof lime, magnesia and alkali system and 99% for sample (g) of tourmalinecomposite disc combined with the low melting point glass of thezinc-alkali system. Further, far infrared emissivity at 4 μm (6-7 μm atroom temperature) is 30%, 50% and 75% for the three samples.

Tourmaline is a far infrared radiator, while the low melting point glassis also a far infrared radiator having higher emission intensity. Then,the far infrared emissivity of tourmaline composite at room temperatureis increased largely by combining tourmaline with the low melting pointglass. The magnitude of far infrared radiations at room temperature issomewhat lower (80% at 10 μm for a black body), but it increases by10-15% when combined with low melting point glass powders.

As explained above, in this embodiment, low melting point glass powders,having a similar composition and having a melting point below thetemperature at which the crystal structure of tourmaline is destroyed,are mixed with as much pulverized tourmaline as possible, and arecrushed as finely as possible in a wet pulverizing process. The obtainedwater-including material is formed and sintered at a temperature alittle lower than the melting point of the glass powders. Thus,tourmaline composite grains can be produced which increase the electricpotential and far infrared emissivity of natural tourmaline to apractical level.

Far infrared rays serve the function, by being absorbed in waterclusters. If the radiation wavelength of far infrared rays agrees withthe absorption wavelength of an object to be irradiated, molecules inthe object absorb the radiations at that wavelenght causing stretchingand deformation due to the resonance and the molucules are brought to astate where it becomes easier to react and to generate heat. An objectto be radiated is usually water, and a cell contains about 70% of water.Thus, the absorption curve of water has been studied well. FIG. 13 showsa spectral transmittance curve (far infrared absorbance curve) of water.Water has absorption wavelengths at 3 μm, 6-7 μm and above 10 μm. On theother hand, a tourmaline composite has absorption wavelengths at 6-7 μmand above 10 μm. When a tourmaline composite is put in water, waterabsorbs wavelengths of 6-7 μm and above 10 μm to perform molecularmotions actively. Usually water consists of clusters of 36-37 molecules,but those are divided into clusters of 7-8 molecules and the reactivityis increased by absorbing far infrared rays. It is said this is thelargest advantage of far infrared rays to water. Further, as otheradvantages of cluster division, impurities included are sent out,solubility is increased, surface tension is decreased, vaporization isenhanced, and these effects can be used for various uses.

Therefore, when tourmaline composite grains of the embodiment areimmersed in water, they produce as ionization effect including mainlywater electrolysis due to the electric potential and an enhancedradiation effect of far infrared rays. The enhanced radiation effect offar infrared rays facilitates decomposition of organic substances byradiating directly to organic substances (oils and amines) of the livingbody dissolving in water, and helps soap function due to OH⁻ ionsproduced by the ionization of water by tourmaline itself. Thus, in thisembodiment, the weak electric potential of tourmaline is increased to apractical level to accelerate ionization of water and washing effectsuch as oil decomposition in water is enhanced due to the properties offar infrared rays. As explained above, besides the ionization,tourmaline functions to enhance reactivity by dividing water clustersdue to far infrared rays, and the synergy thereof helps to activatewater. Thus, without adopting the surface activation theory of H₃ O₂ ⁻,the washing effect of tourmaline can be explained. It is also acharacteristic that the energy for the washing is due to the energy oftourmaline itself.

A circulation hot bath (24-hour hot bath) is one of the expected uses oftourmaline. It becomes popular in several years. Recently, a biologicalfilter, an ultraviolet light or the like is built in a circulation pathof hot water for recycling, sterilizing and removing waste. Thus, aperson can use the hot bath always, and the frequency of waterreplacement is once in one to four weeks. In many circulation hot baths,crushed materials of hydrothermal metamorphism rocks or pegmatiteminerals are pulverized or are set for passing hot water therethrough,as an assistant to filtration, or to add hot spring ingredients.

Table 1 shows a result of water quality tests for hot water (40° C.)used for half a month in a circulation hot bath (300 liters) for homeuse wherein 1 kg of tourmaline synthetic grains are filled in a part ofcirculation. Thus, even when hot water is used continuously for half amonth, turbidity is kept low, and the amount of organic substances (OCD)is kept small. That is, there is no problem in the water for the bath.

                  TABLE 1                                                         ______________________________________                                        Water quality                                                                                     Water used   Water used                                           Water used  for 15 days  for 15 days                                  Item    for 1 day   (1)          (2)                                          ______________________________________                                        Cl      8.2         9.7          9.7                                          Ca      11          12           12                                           Na      11          13           14                                           Fe      Not detected                                                                              Not detected Not detected                                 1)      1.9         2.3          3.0                                          turbidity                                                                             <1 degree   <1 degree    <1 degree                                    2)      Not detected                                                                              Not detected Not detected                                 pH       7.29        7.17         7.13                                        3)      154.3 (19.1° C.)                                                                   186.4 (18.2° C.)                                                                    187.9 (24° C.)                        B        0.027       0.98         0.88                                        ______________________________________                                    

NB: In Table 1, "1" denotes organic-substance (COD), "2" denotes numberof coliform bacillus groups, and "3" denotes electrical conductivity.

When the tourmaline composite grains are filled for the abovecirculation hot bath, they function as an assistant for recycling thehot water due to the synergetic function of far infrared rays andionization.

(1) Far infrared rays are radiated at the absorption wavelengths of 7-8μm of dirt (proteins and substances decomposed from fatty acids) in hotwater to facilitate decomposition.

(2) Dirt is decomposed due to OH⁻ in water increased by the electricalpotential of tourmaline.

Another characteristic of tourmaline when used in the circulation hotbath is that the blood flow is enhanced due to electrical stimulus tothe skin of a person in the hot bath because the weak current in wateradjacent to the tourmaline grains is about the same as the current incells of the person. Thus, so-called chill after leaving a hot bathbecomes hard to occur.

Next, an embodiment of an apparatus 101 for supplying wash water isexplained. As shown in FIG. 14, the apparatus 101 includes a raw watertank 102 for storing raw water, an activated water tower 103 foractivating water (that is, for supplying water rich in OH⁻ ions andrelatively small clusters) by converting the raw water, and a pressurepump (or compressor) 104 for transferring the raw water in the tank 102to the activated water tower 103. The tank 102 is made of steel platesand mounted on a base 105. Raw water is introduced through an inlet 106into the tank 102. The inner face of the tank 102 is subjected tocoating or lining with a resin or the like in order to improve corrosioninhibition. Raw water is for example tap water, underground water orwell water. The material of the tank 102 is not limited to steel plates,and any material can be used as far as the strength is sufficient (forexample, so as not to destroy the tank until the inner pressure in thetank is increased up to about 2 kg/cm²).

The activated water tower 103 is also mounted to the base 105. The tower103 has an outer tube 107 of hollow cylinder made of steel plates. Aninlet 108 provided at the bottom end wall 107a of the outer tube 107 isconnected through a supply tube 110 to an outlet 109 of the raw watertank 102 provided at the bottom 102a thereof. Further, an outlet 111 isprovided at the top wall 107b of the tower 103 to supply activatedwater. The outer tube 107 is fixed with fixing members 112 and 113 tothe raw water tank 102.

Inside the outer tube 107, five inner tubes 114 of hollow cylinders arestacked in multi-stages. Many tourmaline composite grains 115 havingshapes of beads or balls are contained inside the inner tubes 114, asshown schematically in FIG. 14. The grains 115 are made of finetourmaline powders combined with a binder of low melting point glass asexplained above. As the glass, the low melting point glass powdersincluding zinc explained above are used.

As shown in FIGS. 15 and 16, the inner tube 114 is made of a tube part116 made of a plastic material and having a form of a hollow cylinder,and a base plate 118 made of punching metal, fixed to the bottom of thetube part 116 and having many openings 117. Each opening 117 isrectangular, and its shorter side is smaller than the diameter of thetourmaline composite grains so as for them not to pass therethrough.Further, a handle 119 is fixed to the inner tube 114 (tube part 116) forcarrying the inner tube easily. The tube part and the bottom of theinner tube 114 may be made of a plastic material as an integral productwithout using punching metal. The lowest inner tube 114 among the fivestacked inner tubes is arranged above the bottom wall 107a of the outertube 107 on a spacer 120. The spacer 120 is set in order to introducethe raw water received through the inlet 108 in the outer tube 107, intothe lowest inner tube 114 uniformly.

The pressure pump (compressor) 104 is put on the top wall 102b of theraw water tank 102, and air pressurized by the pump 104 is introducedthrough a path 121 into an air portion 122 in the tank 102. When rawwater in the tank 102 is supplied to the activated water tower 103, theinlet 106 is closed with a valve (not shown), and the pressurized air issupplied by the pump 104 in the tank 102. Thus, the air pressure in theair portion 122 presses the raw water in the tank 102 toward theactivated water tower 103. The air pressure in the air portion 122 isfor example 1.5 kg/cm².

In the tower 103, the raw water introduced from the tank 102 isconverted to activated water by contacting with the tourmaline compositegrains 115 inside the inner tubes 114. In each inner tube 114, the rawwater flows upward. This flow moves the grains 115 vigorously, and thetourmaline composite grains 115 form a fluidized layer in the inner tube114. Thus, friction contact of water with the grains or friction contactbetween the grains is accelerated, and the conversion from raw water toactivated water is improved.

The mechanism on the conversion of raw water to activated water isrepeated briefly here. A part of H₃ O⁺ ions (hydronium ions) produced byionization of water contacts with a metal or plastic (resin) of theinner tubes 114 and vanishes by losing the positive charge. This actionis apparent especially for the plastics as the material of the tubeportion 116 of the inner tube 114 because negative charges are generatedon the plastic surface by the friction contact with water, and thenegative charges neutralize the positive charges of H₃ O⁺ ions todecrease the H₃ O⁺ concentration. Thus, water includes many OH⁻ ions (orH₃ O₂ ⁻ ions). Further, when H₃ O⁺ contacts with a iron surface, theiron receives the positive charge to become Fe²⁺ and Fe³⁺ to get rusty,but the resultant FeO and Fe₂ O₃ are combined to form a coating film ofmagnetite (Fe₃ O₄). Thus the H₃ O⁺ is consumed so that iron becomes inthe passive state to prevent further corrosion. As explained above, OH⁻ions generated by the tourmaline composite grains 115 increase thewashing performance of water. As explained above, far infrared raysemitted from the tourmaline composite grains 115 are absorbed by waterto divide clusters into relatively small clusters of 7-8 watermolecules. Further, as secondary effects, impurities included are sentout, solubility is increased, surface tension is decreased, andvaporization is enhanced. These effects enhance the washing performanceof the activated water.

Further, because the binder in the tourmaline composite grains includesa zinc component (Zn), a very small amount of zinc is dissolved in waterfrom the tourmaline composite grains in the activated water tower 103,and the wash water includes the very small amount of zinc. When astructure such as an automobile, a railroad train, an airplane or anouter wall of a building exposed to outdoor environment is washed withthe wash water, zinc included in the wash water deposits by a very smallamount in very small recesses on the surface of the structure and itbecomes zinc oxide ZnO. When ZnO, which is a semiconductor, receivesultraviolet rays in sunlight, the electrical conduction occurs torelease the electrostatic charges on the surface or removes them. Thus,the surface becomes hard for dust or the like to adhere thereto.

Further, because tourmaline or the binder in the grains include boron(B), a very small amount of boron is dissolved in water from thetourmaline composite grains in the activated water tower 103, and thewash water includes the very small amount of boron. When a structure iswashed with the wash water, boron included in the wash water deposits bya very small amount on the surface of the structure to form a thincoating (coexistence of ZnO). The boron coating protects the surface ofthe structure, and increases the luster of the surface. Thus, the lusteror the beauty of the structure is improved.

As explained above, raw water is converted to activated water in theactivated water tower 103, and the activated water is supplied from thetower 103 as wash water. By using the activated water as wash water,various structures such as an automobile or an outer wall of a buildingcan be washed effectively without using a detergent.

Various advantages are observed when the wash water is used.

(a) A detergent or a drug for washing is not needed. washing isperformed only with a physical technique such as brushing. Therefore,the surface of a structure is not changed in quality nor is itdeteriorated, and the water does not become dirty. Washer's hands arenot harmed.

Further, washing operation becomes simple, and washing cost isdecreased.

(b) Green moss or the like does not grow on the surface of a structureafter washing.

(c) Electrostatic charges on the surface of a structure are removed byzinc oxide deposited on the structure, and dirt or the like becomesharder to adhere to the surface.

(d) The luster of the surface of a structure becomes better by borondeposition on the surface, and waxing is not necessary.

Table 2 shows an example of water compositions in the units of mg/literof raw water (well water in this example) and activated water obtainedfrom the raw water.

                  TABLE 2                                                         ______________________________________                                        Composition of well water and washing                                         water (activated water)                                                       Component                                                                     (mg/liter)    Activated water                                                                          Well water                                           ______________________________________                                        Zn            0.11       0.005                                                B             0.34       0.02                                                 Na            11         10                                                   K             4.9        4.9                                                  Mg            9.1        9.1                                                  Ca            0.88       0.94                                                 SiO.sub.2     20         20                                                   Mn            0.08       0.12                                                 Cl            6.8        6.8                                                  NO.sub.3      0.23       0.15                                                 SO.sub.4      6.1        6.2                                                  ______________________________________                                    

As mentioned above, various structures such as a motor vehicle or anouter wall of a building can be washed effectively with the activatedwater, without using a detergent. Further, water can be recycled forwashing. As an example, FIG. 17 shows an apparatus 201 for a motorvehicle 202 which supplies wash water by recycling. The object to bewashed is not limited to the motor vehicle.

The apparatus 201 has a waste water reservoir 203 which stores wastewater after washing a motor vehicle 202 such as an automobile, a watertank 204 which controls the concentrations of dirt contents included inthe waste water introduced from the waste water reservoir 203 at aconstant level, a second tower 205 which decomposes organic substancesin the water received from the water tank 204 to purify the water, and afirst tower or an activated water tower 206 which converts the waterpurified by the second tower 205 to activated water (rich in OH⁻ ionsand including relatively small water clusters) by the tourmalinecomposite grains and supplied the activated water. The water tank 204and the second tower 205 are provided for preprocessing the waste watersupplied for the waste water reservoir 203 before supplying it to thefirst tower 206 for activating the waste water.

The waste water reservoir 203 is a water reservoir made of concrete andbuilt underground. The waste water reservoir 203 has a top cover 207which closes the top end thereof, and the top cover has a member 207afor collecting waste water after washing. A first pump 208 sends thewaste water in the tank 203 through a supply pipe 209 to the water tank204 for controlling concentration. A filter 210 is provided at an inletend of the first pump 209 and it removes dirts such as solid substancesand oil floating in the waste water. A valve 211 is provided at anoutlet end of the supply pipe 209 for opening and closing the pipe.Further, a fence 212 is set in the reservoir 203 near the inlet end ofthe first pump 208 or the filter 210 in order to remove oil floating inthe water. A discharge path 245 is provided to discharge the waste waterin the reservoir 203 to the exterior of the system.

The waste water tank 204 for controlling the concentration has asupplier 246 for supplying virgin water (such as tap water or wellwater) into the water tank 204. According to the concentration of theimpurities included in the waste water in the water tank 204, a valve247 is opened or closed to add virgin water to the waste water. Anoutlet is provided at the lower portion of the water tank 204, and thewaste water, after controlling the concentration, is introduced by asecond pump 224 through a path 249 with a valve 248 to the second tower205 for decomposing organic substances.

As shown in FIG. 18, the second tower 205 has an outer tube 213 havingthe shape hollow cylinder and made of steel plate. The outer tube 213contains a radiation processor 214 at the lower part and a biologicalprocessor 215 at the upper part. It is desirable that the distancebetween the two processors 214 and 215 be separated as far as possible.The radiation processor 214 has a tray 216 made of a plastic material,and the tray 216 has a tapered section extending upward and acylindrical section contained closely to the outer tube 213. The tray216 contains many grains 217 which include very fine natural radiatorsubstances combined with a binder. The natural radiator substance is forexample a rare earth mineral which generates radiations naturally. Thegrains 217 are hereafter referred to as natural radiation sourcecomposite grains. The materials of the outer tube 213 and the tray 216are not limited to the above ones. For example, the outer tube 213 maybe made of a plastic material, or the tray 216 may be made of a metal.The form of the radiation processor 214 is not limited to the above one,and the inner tubes 114 for holding tourmaline composite grains asexplained above may be used therefor.

The second or organic substance decomposition tower 205 has an inlet 218at its lower side for introducing the waste water after concentrationcontrol, and the inlet 218 is connected through an L-shaped pipe 219 tothe downstream side of the path 249. Therefore, the waste water afterconcentration control in the water tank 204 is introduced through thepath 249 and the pipe 219 to the radiation processor 214, and it flowsupward in the tray 216 to contact with the natural radiation sourcecomposite grains 217. Thus, the grains 217 are fluidized vigorously bythe upward flow of the waste water to accelerate the contact thereofwith the waste water. Thus, the decomposition of the organic substancesin the waste water is accelerated.

In the radiation processor 214, OH⁻ ions and OH radicals are producedfrom water molecules in the waste water by radiations (α, β, γ rays)radiated from the natural radiator substances in the natural radiationsource composite grains 217, and they decompose organic substances (oil,fat, protein and the like). Further, far infrared rays radiated from thegrains 217 divide water clusters in the water, and organic substancescontained in the clusters therein are let out, and this also acceleratesthe decomposition of organic materials by the radiations.

The biological processor 215 mounted above the radiation processor 214has an upper porous plate 221, a lower porous plate 222 and a biologicalfilter 223 between them. The porous plates 211 and 222 are fixed to theouter tube 213 with brackets 220. The biological filter 223 comprises ahoneycomb or fibrous base made of a plastic material or the like and amicroorganism film on the base. The microorganism film includes manyaerobic bacteria. The waste water processed by the radiation processor214 to decompose organic substances rises in the outer tube 213 to passthrough the biological processor 215. The organic substances which havenot been decomposed by the radiation processor 214 are decomposed by theaerobic bacteria biologically when they pass through the biologicalprocessor 223.

The waste water purified by the radiation and biological processors 214,215 by decomposing organic substances is supplied through a supply path225 to the first or activated water tower 206. A valve 226 is providedat an outlet side of the supply path 225 for opening or closing the path225.

As shown in FIG. 19, the first tower 206 has a similar structure to theactivated water tower 103 shown in FIG. 14. The first tower 206 has anouter hollow cylindrical tube 227 made of steel plates. A first inlet228 provided at the lower side of the outer tube 227a is connected tothe down stream end of the supply path 225 to introduce waste water fromthe second tower 205. Further, at a second inlet 229 provided at thelower side of the outer tube 227a is connected to another supply path230 for introducing tap water as virgin water, and a valve 231 isprovided to open or close the supply path 230. Thus, tap water can beintroduced into the first tower 206. Underground water or well water maybe used as virgin water instead of tap water. Further, an outlet 232 isprovided at a top wall 227b covering the outer tube 227 to send theactivated water, and a hose 233 is connected to the outlet 232 forsupplying the activated water.

Inside the outer tube 227, five inner tubes hollow cylindrical tube 234are stacked in multi-stages. Many tourmaline composite grains 235 havingshapes of beads or balls are contained inside the inner tubes 234. Thegrains 235 are made of fine tourmaline powders combined with a glassbinder as explained above. The functions of the grains are explainedabove, and the explanation thereof is omitted here. The inner tubes 234are similar to the inner tubes 114 shown in FIGS. 15 and 16. The waterintroduced into the first tower 206 is activated as explained above onthe activated water tower 103, and the detailed explanation is omittedhere.

The waste water supplied from the second tower 205 or tap water isconverted to activated water in the first tower 206, and the activatedwater is used as wash water. That is, when an automobile 202 is washedby a washing machine 242, a valve 241 provided in the hose 233 isopened, and the automobile 202 is washed by the washing machine 242 withthe wash water (activated water) supplied from the first tower 206. Thewashing machine 242 washes the automobile with water by using a physicalmeans, without using a detergent. In this example, the washing machine242 washes the automobile with brushing. The blast pressure of the washwater depends on the discharge pressure of the second pump 224 or thesupply pressure of tap water. When the automobile 202 is subjected forfinal washing, it is desirable to introduce tap water to the first tank206 in order to supply wash water having high washing performance.

An analysis of the activated water which have been purified andconverted as explained above shows that it is perfectly transparent, andthe remains after evaporation is 87 mg/liter. The activated waterincludes calcium, magnesium, sodium and silica somewhat, but it does notinclude iron. The analysis result means that the wash water has similarwater quality as tap water as far as the above components are concerned.

Washing effect is compared in a gate-type washing machine for motorvehicle. An automobile is washed with (a) brushing and waxing usingunderground water, (b) brushing using the activated water and (c)brushing using underground water. Table 3 summarizes the results. Theluster of the automobile after washing is measured with a luster meter(Minolta GM-60). It is apparent that the brushing using the activatedwater according to the embodiment of the invention is far superior thanthe prior art brushing with underground water and has a similar effectas the prior art washing with brushing and waxing.

                  TABLE 3                                                         ______________________________________                                        Luster of automobiles after washing                                           Washing process   Luster                                                      ______________________________________                                        Underground water +                                                                             170                                                         brushing and waxing                                                           Activated water + 165                                                         brushing                                                                      Underground water +                                                                             123                                                         brushing                                                                      ______________________________________                                    

NB: Luster is measured with Minolta GM-60.

The washing of automobile with the above-mentioned apparatus 201 has thefollowing advantages.

Because the waste water after washing is recycled by decomposing organicsubstances, consumption of water for washing moving vehicles isdecreased to a large extent, and the water resources can be saved.

Because the activated water obtained by activating waste water afterwashing has a similar washing performance as a detergent, it is notnecessary to use a detergent, and a moving vehicle can be washedefficiently only with a physical means such as brushing with water.Therefore, even if washing is repeated, the coating on the surface ofthe body of a moving vehicle is not changed in quality or is notdeteriorated, and the water does not become dirty. Washer's hands arenot harmed. Further, washing operation becomes simple, and washing costis decreased. Because no microorganisms grow in the activated water,green moss or the like does not grow on the surface of the body.Further, as explained above, zinc included in the binder preventsadhesion of dirts on the surface of the body, and boron included intourmaline and the binder protects the surface of the body. Because thefilm including boron enhances luster of the surface, the luster or thebeauty of the body becomes good even without waxing.

Although the present invention has been fully described in connectionwith the preferred embodiments thereof with reference to theaccompanying drawings, it is to be noted that various changes andmodifications are apparent to those skilled in the art. Such changes andmodifications are to be understood as included within the scope of thepresent invention as defined by the appended claims unless they departtherefrom.

What is claimed is:
 1. A tourmaline composite grains comprising:a glassmatrix; and powders of tourmaline dispersed therein in an amount equalto or larger than 30% by weight.
 2. The tourmaline composite grainsaccording to claim 1, wherein said glass matrix is made of glass havingmelting point between 500° C. and transition temperature of tourmaline.3. The tourmaline composite grains according to claim 2, wherein saidglass matrix comprises a glass component having far infrared emissivityhigher than tourmaline.
 4. A method for producing tourmaline compositegrains comprising the steps of:pulverizing tourmaline to provide powdersthereof; mixing the tourmaline fine powders with glass powders havingmelting point between 500° C. and transition temperature of tourmalineto provide a mixture; forming the mixture into grains; and sintering thegrains at a temperature below melting point of the glass powders.
 5. Themethod according to claim 4, wherein the grains are sintered in atemperature between 450 and 800° C.
 6. The tourmaline composite grainsaccording to claim 1, wherein the weight ratio of the tourmaline powdersis equal to or smaller than 70%.